1317 Index A activation enthalpy 23, 39, 188, 195–196, 204, 205, 206, aaptosine 358, 359 217, 339, 341, 345, 370, 393, 398, 411, 412, 443, 444, ab initio Hartree–Fock (HF) calculations 273 452, 453, 462, 465, 500, 697, 728 absolute asymmetric synthesis 634, 635 activation entropy 39, 188, 190, 192–196, 198, 369, 500, absolute electronegativity 37 689, 695, 872 absolute hardness 37–39, 839 activation entropy and reaction mechanism absolute softness 37 – Cope rearrangement 195 absorbance 616 – gas phase – – homolysis and radical combination 192–193 absorption complex 624, 667 – – isomerizations 193–194 absorption on crystalline quartz 44 – neighboring group directing effects 197 acetaldehyde 15, 18, 60, 66, 70, 80, 82, 86, 145, 146, 147, – retro-carbonyl-ene reaction 195–197 195, 197, 223, 514, 551, 619, 683, 686, 697, 732, 797, activation parameters 819, 855, 920, 921, 1168 – Curtin–Hammett principle 190–192 acetamide 62, 66, 82, 89, 619 – temperature effect, two parallel reactions 190 acetic acid 12, 13, 49, 60, 87, 89, 151, 373, 503, 619, 650, acyclic ,-and,-enones 60, 642 699, 800, 808, 900, 1030, 1032–1034, 1050 acyclic alkylaminocarbene 439 acetic anhydride 12, 61, 216, 619, 802, 1033 acyclic diene 55, 468, 633, 1126 acetone 15, 25, 35, 36, 60, 70, 80, 85, 86, 88, 90, 122, acyclic 1,3-dienes 55, 697, 698 143, 146–148, 153, 203, 210, 213, 224, 226, 229–232, acyclic dithiosilylene 448 373, 374, 382, 383, 412, 413, 435, 619, 622, 623, 628, acyclic peroxides 729 633, 637, 638, 641, 656, 662, 669, 671, 682, 685, 686, (1,2)-acyloxy shifts 458 688, 722, 732, 733, 837, 878, 897, 1057, 1066, 1067, acyl group transfers 209, 212, 221, 798–810 1069, 1107 acyl transfers 209–211, 213, 799, 802–807, 810 acetophenone 82, 715, 725 3,3-(adamant-2-yl)-3H-diazirine 652 5-acetoxy- and 5-chlorocyclopentadiene 408 (adamant-1-yl)nitrene 662 acetoxypyranone 433 addition acetyl chloride 11, 63, 619 – of alkylzinc reagents 1142–1143 acetylenes, Pd-catalyzed carbonylation of 1043 – of Grignard reagents 1136–1142 – of organoaluminum compounds 1143–1145 acetylide anions 1124 – of organoboron 1145–1148 achiral alkene 703 – of silicium 1145–1148 achiral allenamide 433 – of zirconium compounds 1145–1148 acid catalyzed cationic cyclization 383 addition–elimination mechanism 238, 658, 922, 923, acid-catalyzed (2+2)-cycloadditions 853, 855 1134, 1180 acid or base-catalyzed acyl transfers 799–802 additivity rules acrolein 8, 304, 393, 401, 402, 433, 520, 827, 921, 1074 – ,-unsaturated carbonyl compounds 130 acrylic derivative 20, 39, 130, 501, 717, 796, 825 – atropisomerism in 1,3-dienes and diaryl compounds acrylic ester 8, 60, 372, 387, 406, 426, 674, 826, 827, 129–130 1041, 1060, 1067, 1081, 1142, 1175 – conjugated dienes and diynes 127–129 acrylonitrile 8, 40, 62, 369, 393, 399, 430, 507, 667, 676, – molecular groups 678, 681, 682, 824, 826, 1074, 1081 – – additivity of, molecular properties 110 Organic Chemistry: Theory, Reactivity and Mechanisms in Modern Synthesis, First Edition. Pierre Vogel and Kendall N. Houk. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2019 by Wiley-VCH Verlag GmbH & Co. KGaA. 1318 Index additivity rules (contd.) – hydroacyclation of 1064 – – group additivity methods 110 – hydroarylation of 1057–1060 – – toluene formation 111 – hydrocyanation of 1066–1067 – oximes 136 – hydroformylation of 1034 – standard entropy increments 113–114 – hydrosilylation 909–910 – standard group equivalents 111–113 – intermolecular hydroacylation of 1064, 1068 – steric effects – isomerization 848 – – allylic 1,3-strain 126, 127 – metallacarbation 1055 ––anti-Bredt alkenes 125–126 – metathesis 1126–1131 – – Bredt’s rule 125, 126 – Pd(II)-mediated oxidative carbonylations 1042–1043 – – cyclobutane 118–119 alkene–silver cation complex 210 – – cyclohexane 119–121 1-alkenylallenyl silyl ethers 352, 353 – – cyclohexanones 121–122 alkenylbenzocyclobutenes 1112 ––cyclohexene 122 alkenyl cation intermediates 659–660 – – cyclopentane 119, 120 5-alkenylcyclohexa-1,3-dienes 361 – – cyclopropane 118 alkenylidenecyclopropanes 1102 ––(E)- vs.(Z)-alkenes 117 alkenyl mechanism 1031, 1032 – – Gauche interactions 114–117 1-alkoxy-3-acyloxy-1,3-dienes 419 – – medium-sized cycloalkanes 122–124 1-alkoxyalkyllithium 460 – – polycycloalkanes, conformations and ring strain 1-alkoxy- and 1-halogenophospholes 137 124 1-alkoxy-1,3-bis(silyloxy)-1,3-butadienes 411 – – ring strain and conformational flexibility 117, 118 alkoxy radicals 69, 72, 75, 690, 1123 – – ring strain in cycloalkenes 125 alkoxy-substituted aldehydes 845 – translational entropy on equilibria alkyl -D-glucopyranosides 143 – – ageing of wines 148, 149 alkylaluminum halides 848 – – aldol reaction 146–148 alkyl arylaminoacetate 649 – – and crotonalization reactions 146–148 alkyl aryloxyacetate 649 adiabatic transition 21, 617, 711 alkylate technology 1055 adsorption on achiral surfaces 44 alkylation, of alkanes 1054–1056 aerobic C–H oxidations 914–917 alkyl azides 662 aerobic didehydrogenative coupling reaction 1029, alkyl disubstituted silylene 448 1116 alkyl halides ageing of wines 148–151 – photolysis of 654–657 alcohols oxidation with molecular oxygen 918–920 – reduction of 906–907 alcoholysis 431, 798, 800, 806 alkylidene carbenes 384, 461, 630 aldehydes 13–16, 38, 40, 42, 49, 60, 66, 136, 145–147, alkylidene-2H-pyran (E) 359 157, 212, 218, 219, 222, 224–226, 240, 297, 302–304, 2-alkylideneoxetane 375 380, 382, 383, 385–387, 411–415, 419, 427, 439, 460, alkyl iodides 10, 24, 63, 66, 68, 654, 861, 874, 1136, 481, 493, 494, 502–504, 508–518, 520, 523, 524, 619, 1142, 1151, 1156, 1181 637, 681, 683, 686, 687, 705, 713, 714, 721, 722, 733, alkylithium 380, 1136 796, 810–813, 819–822, 826, 827, 834–838, 840–847, alkyl mechanism 1031, 1032 849–852, 855, 856, 880, 891, 894, 899–902, 905, 907, alkyl/peroxyl 1,4-diradical 696, 705 912, 917–922 3-alkyl-3-phenyl-3H-diazirines 653 Alder endo rule 407, 417, 439 alkyl-substituted alkenes 15, 17, 54, 66, 85, 86, 278, 314, Alder-ene-reactions 501, 502, 504, 515, 796, 838, 844, 624, 626, 700 848–851, 1054, 1056–1057 alkyl-substituted alkynes 55, 56, 67, 630 – of unactivated alkynes and alkenes 1056 alkyl-substituted 1,2-dioxetane 732 aldol and crotonalization reactions 146–148, 514 alkylzinc reagents, addition of 1142–1143 aliphatic alkylation 1055 alkyne/alkene cross-metathesis 1130, 1132 alkanes, dehydrogenation of 897 alkynes alkenes –Cu2+-catalyzed oxidative homocoupling of 1117 – enantioselective carbomagnesiation 1140 – heterogeneous catalysts for 892–894 – heterogeneous catalysts for 892–894 – hydroacylation of 1064 – homogeneous catalysts for 894–897 – hydroarylation of 1060 Index 1319 – hydrocyanation of 1066–1067 -ionone 153 – hydroformylation of 1038 -ketoaziridines 716 – hydrogenation, homogeneous catalysts for 894–897 -ketoepoxides 716 – hydrogenation of 897–899 -methoxydibenzyl ketone 431 – metathesis 889–890, 1133–1134 -methylbenzyl azide 662 – oxidative aminoalkylation of 1123–1124 -pyridones 64, 137, 1097 – palladium-catalyzed hydroalkenylation of 1063 -pyrones 289, 391, 1097, 1102 – polymerization 887–890 -santonin 615 – Ru-catalyzed (2+2)-cycloadditions of 1080 -silyl stabilized carbanions 385 – silylformylation 1039–1041 -stannylated thionocarbamates, alkynylation of 1161 – Zr-catalyzed ethylalumination 1144 ambimodal transition states 703 – Zr-catalyzed methylalumination 1144 amines 713 allenamides 433, 670, 671, 1104 – and carboxylic acids 807, 810 allene–alkene intermediates 430 1-aminoadamantane 662 allene cycloaddition 372–373 amino-alcohols 427, 802 allowed (CO) → *(CO) transition 620 aminoalkyl radical 69, 70, 719, 721, 724, 1123, 1124 allowed thermal [4c] electrocyclization 632 2-amino-, 4-aminophenones 649 allowed transitions 619 aminoarenethiolate 925 allylcyclopropane 669 2-aminodiene 414, 828 allylic alcohol 153, 197, 209, 210, 213, 224, 226, 359, 5-aminopenta-2,4-dienal 646 382, 408, 470, 472, 483, 491, 505, 702, 703, 845, 892, aminophenols 513, 667, 925 900, 901, 1076, 1118, 1169 3-aminophthalate salt 730 allylic alkylation 211, 240, 1168–1171 ammonium detergents 114 allylic boron compounds 845 amphoteric compounds 798, 800, 802 allylic cations 76, 79, 279, 490, 1103, 1104 1,2- and 1,4-dihydroarenes 724 allylic hydroperoxides 505, 688, 697, 700, 702, 703 1,2-, 1,3- and 1,4-dimethylbenzene 729 allylic hydroxy group 685 2-, 4-, and 5-methylpyrimidines 647 allylic 1,3-strain 126 1,2,3- and 1,2,4-triphenyltrichlorobenzene 429 allyl methyl thioether into methyl (E)-prop-2-en-1-yl Anelli–Montanari protocol 918 thioether 133 anharmonicity 49, 192 allyl/peroxyl diradical 696, 697, 705 anhydride formation 12 allyl -molecular orbitals 282 anilines 28, 35, 36, 62, 88, 89, 237, 239, 415, 649, 661, allyl (prop-2-enyl) ethers 133 667, 803, 813, 852, 1060, 1182, 1184 allylsilanes synthetic 843 annulation reaction 1081, 1115, 1189 ,′-dibromoketones 432 annulenes 132, 144, 299–301, 366 -amino acids 213 anodic oxidation of N-aminophthalimide 441 -arylation of carbonyl compounds and nitriles 1187 antarafacial [6a+2s]-cheletropic additions 445 ,-epoxyketones 153 antarafacial/suprafacial [ 4a+2s]-cycloaddition 367 ,-unsaturated aldehydes 60, 67, 414 anthelmintic (toxic) drug 695 ,-unsaturated carbonyl compounds 60, 130, 414, anthracene-9,10-dicarbonitrile (DCA) 691, 707, 716 628, 642 anthracenemagnesium 1136 ,-unsaturated nitriles 40, 62, 86, 392, 682 anti-AIDS 217 -chlorocyclohexanone 431 antiaromatic cyclopentadienone 615 (–)--cuprarenone 376 antiaromaticity 27, 36, 109, 113, 131, 144, 271, 284, -cuprarenone/-cycloeliminations 886 286–288, 292, 306,